Bis(ferrocenecarbaldehyde thio­semi­carbazonato-κ2 N 1,S)zinc

M R Vikneswaran; Siang Guan Teoh; Ibrahim Abdul Razak; Hoong-Kun Fun

doi:10.1107/S1600536809007363

. 2009 Mar 6;65(Pt 4):m373–m374. doi: 10.1107/S1600536809007363

Bis(ferrocenecarbaldehyde thiosemicarbazonato-κ² N ¹,S)zinc

M R Vikneswaran ^a, Siang Guan Teoh ^a, Ibrahim Abdul Razak ^b, Hoong-Kun Fun ^b,^*

PMCID: PMC2969079 PMID: 21582327

Abstract

In the title compound, [Fe₂Zn(C₅H₅)₂(C₇H₇N₃S)₂], the Cp rings of each ferrocene residue have a nearly eclipsed conformation. The two thiosemicarbazone ligands each coordinate the Zn atom in a bidentate mode via the N and S atoms, thereby defining a distorted tetrahedral environment. N—H⋯S, N—H⋯N, C—H⋯S and C—H⋯N intra- and intermolecular interactions connect the molecules into a two-dimensional array parallel to (010).

Related literature

For general background, see: Quiroga et al. (1998 ▶); Genova et al. (2004 ▶); Melha (2008 ▶). For related structures, see: Palenik (1970 ▶); Haaland & Sikson (1968 ▶); Li et al. (2004 ▶); Latheef et al. (2007 ▶). For the synthesis, see: Mariño et al. (2006 ▶). For the stability of the temperature controller, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

[Fe₂Zn(C₅H₅)₂(C₇H₇N₃S)₂]
M _r = 637.68
Monoclinic,
a = 10.8483 (2) Å
b = 14.7547 (2) Å
c = 16.1686 (2) Å
β = 105.252 (1)°
V = 2496.85 (6) Å³
Z = 4
Mo Kα radiation
μ = 2.29 mm⁻¹
T = 100 K
0.58 × 0.19 × 0.08 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.348, T _max = 0.840
61395 measured reflections
11266 independent reflections
7721 reflections with I > 2σ(I)
R _int = 0.052

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.010
S = 1.06
11266 reflections
332 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.99 e Å⁻³
Δρ_min = −0.64 e Å⁻³

Data collection: SMART (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809007363/tk2381sup1.cif

e-65-0m373-sup1.cif^{(44.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809007363/tk2381Isup2.hkl

e-65-0m373-Isup2.hkl^{(550.9KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H2N5⋯S2ⁱ	0.80 (3)	2.80 (2)	3.4880 (19)	146 (2)
N6—H2N6⋯N2ⁱⁱ	0.81 (3)	2.21 (3)	2.983 (2)	161 (3)
C7—H7A⋯N2ⁱⁱⁱ	0.98	2.56	3.465 (3)	153
C9—H9A⋯S2	0.98	2.73	3.697 (2)	168
C17—H17A⋯S2^iv	0.98	2.70	3.479 (2)	137
C19—H19A⋯N4	0.98	2.51	2.936 (2)	106
N5—H1N5⋯Cg1^v	0.90 (3)	2.85 (3)	3.515 (2)	132 (2)
C6—H6A⋯Cg2^vi	0.98	2.80	3.755 (2)	164
C10—H10A⋯Cg3^vi	0.98	2.93	3.674 (3)	134
C24—H24A⋯Cg4^iv	0.98	2.83	3.629 (2)	139

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) . Cg1, Cg2, Cg3, and Cg4 are the centroids of C20–C24, C15–C19, Zn1,S2,C2,N4,N3 and Zn1,S1,C1,N2,N1 rings, respectively.

Acknowledgments

HKF and IAR thank the Malaysian Government and Universiti Sains Malaysia for the Science Fund grant No. 305/PFIZIK/613312.

supplementary crystallographic information

Comment

Thiosemicarbazones and their metal complexes have been attracting considerable interest due to their biological activities, such as anti-tumor (Quiroga et al., 1998), anti-viral (Genova et al., 2004), anti-fungal and anti-bacterial properties (Melha, 2008). Herein, we report the crystal structure of the zinc(II) complex formed with formylferrocene thiosemicarbazone, (I).

The average Fe—C_ring distances in (I) (Fig. 1) are as expected for a ferrocene derivative [Fe—Cp1(C5—C9) = 2.043 (2) Å, Fe—Cp2(C10—C14) = 2.050 (2) Å, Fe—Cp3(C15—C19) = 2.046 (2) Å and Fe—Cp4(C20—C24) = 2.044 (2) Å] and are within the range of the values in the structures reported by Palenik (1970) and Haaland & Sikson (1968). The torsion angle for a ring-center, a ring-C atom, the corresponding C atom on the opposite ring and its ring center defines the angle of twist of the Cp rings (Palenik, 1970). The average twist angles are 5.4 and 7.7° for Cp1/Cp2 and Cp3/Cp4, respectively, indicating both Cp rings adopt nearly eclipsed conformations. Each of the Cp1/Cp2 and Cp3/Cp4 pairs are nearly parallel [dihedral angle for Cp1/Cp2 = 0.68 (13)° and 1.02 (13)° for Cp3/Cp4] and co-planar [maximum deviation for Cp1 is 0.006 (2)Å for atom C5; for Cp2 is 0.002 (2)Å for atom C13; for Cp3 is 0.005 (2)Å for both atoms C15 and C16; and for Cp4 is 0.004 (3)Å for both atoms C20 and C21].

Each of the two thiosemicarbazone ligands is bidentately coordinated to Zn(II) via the N and S atoms thus forming a distorted tetrahedral environment. The angles around Zn atom ranges from 86.58 (4) to 131.68 (4)°. These chelating ligands form two five membered rings, Zn1S1C1N1N2 and Zn1S2C2N3N4, which are planar with maximum deviation of 0.011 (1) and 0.014 (1) Å, respectively for the Zn atom. The two five-membered rings form a dihedral angle of 77.75 (5)°. Distorted tetrahedral coordination for Zn(II) was also reported by Li et al. (2004) and Latheef et al. (2007). Bond lengths involving the thiosemicarbazone moieties are generally comparable to the corresponding values reported by Latheef et al. (2007) with the exception of C1—N2 which is shorter and N1—N2, Zn1—S2 and C2—S2 which are longer. This observation is probably due to atoms N2 and S2 being involved in intermolecular interactions (Table 1).

The crystal structure is stabilized by N—H···S, N—H···N, C—H···S and C—H···N intermolecular interactions (Table 1). These interactions link the molecules into 2-D arrays parallel to the ac plane (Fig. 2). The crystal structure is further stabilized by the N—H···π and C—H···π interactions (Table 1).

Experimental

Formylferrocene thiosemicarbazone was prepared as described by Mariño et al. (2006). Zn(CH₃COO)₂.2H₂O(0.21 g,1 mmol) dissolved in methanol (60 ml) was added dropwise at room temperature to a mixture of formylferrocene thiosemicarbazone (0.28 g, 1 mmol) and KOH (0.12 g, 2 mmol) in absolute methanol (15 ml). Amorphous orange solids separated out immediately. The suspension was stirred under reflux for 4 h and filtered. After several days, brown crystals were obtained from the filtrate.